Multi-layer golf ball

ABSTRACT

Multi-layer golf balls having a soft, low compression center; a soft, flexible outer cover layer; and a relatively hard, high compression intermediate layer disposed between the center and the outer cover layer are provided. The outer surface hardness of the intermediate layer is greater than that of both the center and the outer cover layer.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of U.S. patent applicationSer. No. 12/493,504, filed Jun. 29, 2009, the entire disclosure of whichis hereby incorporated herein by reference.

FIELD OF THE INVENTION

The present invention generally relates to golf balls, and moreparticularly to golf balls having a soft, low compression center; asoft, flexible outer cover layer; and a relatively hard, highcompression intermediate layer disposed between the center and the outercover layer.

BACKGROUND OF THE INVENTION

U.S. Pat. No. 4,863,167 to Matsuki et al. discloses a three piece solidgolf ball having improved rebound characteristics and a higher initialvelocity which comprises a center portion; an outer layer disposed oversaid center portion; and a cover disposed over said outer layer. It ispreferred for the golf ball to have a higher hardness on the outer layerthan the inner layer.

U.S. Pat. No. 5,048,838 to Chikaraishi et al. discloses a three-piecesolid golf ball comprising a two-piece solid core consisting of an innerlayer and an outer layer and a cover enclosing the core. The Examplesillustrate golf balls wherein the inner core layer has the same hardnessor is softer than the outer core layer, and wherein the covercomposition is softer than both the inner and outer core layers.

U.S. Pat. No. 5,184,828 to Kim et al. discloses a solid three-piece golfball comprising a core assembly provided by an inner core and an outerlayer and a cover characterized by the following features: a) the innercore has a diameter in the range 23-35 mm and hardness (Shore D) in therange 30-62; b) the outer layer has a diameter in the range 36-41 mm andhardness (Shore D) in the range 30-56; c) the golf ball has a maximumhardness (Shore D) in the range of 46-62 at the outer site of the innercore which is located at the interface between the inner core and theouter layer of the golf ball and the hardness then decreases bothinwardly and outwardly. The inner and outer core layers are formed fromrubber compositions comprising 35-50 parts by weight and 25-40 parts byweight, respectively, of co-cross linking agent, such as zincdiacrylate, and zinc dimethacrylate.

U.S. Pat. No. 7,015,300 to Rajagopalan et al. discloses a golf ballincluding a core; a layer disposed about the core having a hardness ofabout 30 Shore D or greater, a flexural modulus of about 1,000 psi toabout 80,000 psi, a thickness of about 0.01 inches to about 0.100inches, and formed from a thermoplastic composition includingp-phenylene diisocyanate; and a cover having a hardness of 20 Shore D orgreater, a flexural modulus of about 1,000 psi to about 30,000 psi, athickness of about 0.01 inches to about 0.05 inches; and formed from athermoset material.

U.S. Pat. No. 6,926,620 to Dalton et al. discloses a golf ballcomprising a core of one or more layers, a cover layer of one or morelayers and a mantle layer disposed between the core and the cover. Themantle layer comprises a thermoplastic material, preferably having ahardness of greater than 60 Shore D and a Bashore resilience of greaterthan 34 and a vicat point of greater then 350° F.

Background references also include, for example, U.S. Pat. Nos.4,714,253 and 5,002,281 to Nakahara et al. and U.S. Pat. No. 5,935,022to Sugimoto et al., U.S. Pat. No. 4,781,383 to Kamada et al., U.S. Pat.No. 4,625,964 to Yamada, U.S. Pat. No. 6,838,519 to Rajagopalan et al.,U.S. Pat. No. 7,005,479 to Morgan et al., and U.S. Pat. No. 6,905,648 toSullivan et al.

SUMMARY OF THE INVENTION

In one embodiment, the present invention provides a golf ball consistingessentially of a center, an outer cover layer, and an intermediate layerdisposed between the center and the outer cover layer, wherein the outersurface hardness of the center and the outer surface hardness of theouter cover layer are less than the outer surface hardness of theintermediate layer. The center is formed from a polybutadienecomposition and has a diameter of less than 1.500 inches and acompression of 50 or less. The intermediate layer has an outer surfacehardness of greater than 60 Shore D and is formed from a polybutadienecomposition having a solid, single core compression of 60 or greater.The outer cover layer is formed from a composition having a flexuralmodulus of 40,000 psi or less. The solid, single core compression of theintermediate layer is at least 25 compression points higher than thecompression of the center.

In another embodiment, the present invention provides a golf ballcomprising a center, an outer cover layer, and an intermediate layerdisposed between the center and the outer cover layer, wherein the outersurface hardness of the center and the outer surface hardness of theouter cover layer are less than the outer surface hardness of theintermediate layer. The center is formed from a polybutadienecomposition and has a diameter of less than 1.500 inches and acompression of 50 or less. The intermediate layer has an outer surfacehardness of greater than 60 Shore D and is formed from a polybutadienecomposition having a solid, single core compression of 60 or greater.The outer cover layer is formed from a composition having a flexuralmodulus of 40,000 psi or less. A first golf ball subassembly consistingof the center, the intermediate layer and any optional layers disposedbetween the center and the intermediate layer has a compression that isat least 10 compression points greater than the compression of a secondgolf ball subassembly consisting of the center and any optional layersdisposed between the center and intermediate layer.

In another embodiment, the present invention provides a golf ballconsisting essentially of a center, an outer cover layer, and anintermediate layer disposed between the center and the outer coverlayer, wherein the outer surface hardness of the center and the outersurface hardness of the outer cover layer are less than the outersurface hardness of the intermediate layer. The center is formed from apolybutadiene composition and has a diameter of less than 1.500 inchesand a compression of from 5 to 40. The intermediate layer has an outersurface hardness of greater than 60 Shore D and is formed from athermoplastic composition having a solid, single core compression of 60or greater. The outer cover layer is formed from a composition having aflexural modulus of 40,000 psi or less. The solid, single corecompression of the intermediate layer is at least 25 compression pointshigher than the compression of the center.

DETAILED DESCRIPTION

The present invention is directed to a golf ball having a soft, lowcompression center; a soft, flexible outer cover layer; and a relativelyhard, high compression intermediate layer disposed between the centerand the outer cover layer. The soft, low compression center, or overallcore in dual-core embodiments, (i.e., the golf ball subassembly to beencased with the intermediate layer) has an outer diameter within arange having a lower limit of 0.500 or 0.750 or 0.800 or 1.000 or 1.200or 1.300 inches and an upper limit of 1.350 or 1.400 or 1.450 or 1.500or 1.530 or 1.550 or 1.580 or 1.600 or 1.630 inches.

The center, or overall core in dual-core embodiments, (i.e., the golfball subassembly to be encased with the intermediate layer) preferablyhas a compression of 70 or less, or less than 70, or 60 or less, or lessthan 60, or 50 or less, or less than 50, or 45 or less, or less than 45,or 40 or less, or less than 40, or a compression within a range having alower limit of 5 or 10 or 15 or 20 or 25 or 30 and an upper limit of 40or 45 or 50 or 60 or 70, and a coefficient of restitution (“COR”) of0.700 or greater, or 0.750 or greater, or 0.770 or greater.

The compression of a golf ball subassembly comprising the center, theintermediate layer and any optional layers disposed between the centerand intermediate layer is the same as or greater than the compression ofa golf ball subassembly comprising the center and any optional layersdisposed between the center and intermediate layer but excluding theintermediate layer itself. Preferably the compression of a first golfball subassembly comprising the center, the intermediate layer and anyoptional layers disposed between the center and intermediate layer isgreater than the compression of a second golf ball subassemblycomprising the center and any optional layers disposed between thecenter and intermediate layer but excluding the intermediate layeritself, and the difference between the compression of the first golfball subassembly and the compression of the second golf ball subassemblyis 10 compression points or more, or more than 10 compression points, or15 compression points or more, or more than 15 compression points, or 20compression points or more, or more than 20 compression points, orcompression points or more, or more than 25 compression points, or 30compression points or more, or more than 30 compression points, or 35compression points or more, or 40 compression points or more, or 50compression points or more, or 60 compression points or more, or 70compression points or more.

The COR of a golf ball subassembly comprising the center, theintermediate layer and any optional layers disposed between the centerand intermediate layer is preferably 0.790 or greater, or 0.805 orgreater, or 0.810 or greater.

The relatively hard intermediate layer has a thickness within a rangehaving a lower limit of from 0.005 or 0.010 or 0.020 or 0.030 or 0.035or 0.040 or 0.050 or 0.060 or 0.070 inches and an upper limit of 0.100or 0.110 or 0.125 or 0.150 or 0.200 or 0.225 inches. The intermediatelayer has an outer surface hardness which is greater than the hardnessof the center, or overall core in dual-core embodiments, (i.e., the golfball subassembly to be encased with the intermediate layer). In oneembodiment, the outer surface hardness of the intermediate layer is 70Shore C or greater, or 75 Shore C or greater, or 80 Shore C or greater,or 83 Shore C or greater, or greater than 83 Shore C, or 85 Shore C orgreater, or greater than 85 Shore C, or 90 Shore C or greater, orgreater than 90 Shore C. In another embodiment, the outer surfacehardness of the intermediate layer is 50 Shore D or greater, or greaterthan 50 Shore D, or 55 Shore D or greater, or greater than 55 Shore D,or 60 Shore D or greater, or greater than 60 Shore D.

The outer surface hardness of a golf ball layer is obtained from theaverage of a number of measurements taken from opposing hemispheres,taking care to avoid making measurements on the parting line of the coreor on surface defects, such as holes or protrusions. Hardnessmeasurements are made pursuant to ASTM D-2240 “Indentation Hardness ofRubber and Plastic by Means of a Durometer.” Because of the curvedsurface, care must be taken to insure that the golf ball or golf ballsubassembly is centered under the durometer indentor before a surfacehardness reading is obtained. A calibrated, digital durometer, capableof reading to 0.1 hardness units is used for all hardness measurementsand is set to take hardness readings at 1 second after the maximumreading is obtained. The digital durometer must be attached to, and itsfoot made parallel to, the base of an automatic stand. The weight on thedurometer and attack rate conform to ASTM D-2240.

Hardness points should only be measured once at any particular geometriclocation.

Each of the center, the intermediate layer, and any optional layersdisposed between the center and the intermediate layer may have a zeroor negative hardness gradient, as disclosed in U.S. Pat. Nos. 7,537,530and 7,537,529; or a very steep gradient, as disclosed in U.S. PatentApplication Publication Nos. 2008/0161130, 2008/0161132, and2008/0161133, optionally produced through the use of a resorcinolcompound, as disclosed in U.S. Pat. No. 7,544,730; and the layers mayhave opposing gradients, as disclosed in U.S. Pat. Nos. 7,429,221 and7,410,429. The entire disclosure of each of these references is herebyincorporated herein by reference.

For purposes of the present disclosure, a hardness gradient of a golfball layer is defined by hardness measurements made at the outer surfaceof the layer and the inner surface of the layer. “Negative” and“positive” refer to the result of subtracting the hardness value at theinnermost surface of the golf ball component from the hardness value atthe outermost surface of the component. For example, if the outersurface of a solid core has a lower hardness value than the center(i.e., the surface is softer than the center), the hardness gradientwill be deemed a “negative” gradient.

Hardness gradients are disclosed more fully, for example, in U.S. patentapplication Ser. No. 11/832,163, filed on Aug. 1, 2007; Ser. No.11/939,632, filed on Nov. 14, 2007; Ser. No. 11/939,634, filed on Nov.14, 2007; Ser. No. 11/939,635, filed on Nov. 14, 2007; and Ser. No.11/939,637, filed on Nov. 14, 2007; the entire disclosure of each ofthese references is hereby incorporated herein by reference.

In one embodiment, the center is formed from a rubber-based compositioncomprising a base rubber, an initiator agent, a coagent, and optionallyone or more of a zinc oxide, zinc stearate or stearic acid, antioxidant,and a soft and fast agent. Suitable base rubbers include natural andsynthetic rubbers including, but not limited to, polybutadiene,polyisoprene, ethylene propylene rubber (“EPR”), styrene-butadienerubber, styrenic block copolymer rubbers (such as SI, SIS, SB, SBS,SIBS, and the like, where “S” is styrene, “I” is isobutylene, and “B” isbutadiene), butyl rubber, halobutyl rubber, polystyrene elastomers,polyethylene elastomers, polyurethane elastomers, polyurea elastomers,metallocene-catalyzed elastomers and plastomers, copolymers ofisobutylene and para-alkylstyrene, halogenated copolymers of isobutyleneand para-alkylstyrene, copolymers of butadiene with acrylonitrile,polychloroprene, alkyl acrylate rubber, chlorinated isoprene rubber,acrylonitrile chlorinated isoprene rubber, and combinations of two ormore thereof. Diene rubbers are preferred, particularly polybutadiene,styrene-butadiene, and mixtures of polybutadiene with other elastomerswherein the amount of polybutadiene present is at least 40 wt % based onthe total polymeric weight of the mixture. Particularly preferredpolybutadienes include high-cis neodymium-catalyzed polybutadienes andcobalt-, nickel-, or lithium-catalyzed polybutadienes. Suitable examplesof commercially available polybutadienes include, but are not limitedto, Buna CB high-cis neodymium-catalyzed polybutadiene rubbers, such asBuna CB 23, and Taktene® high-cis cobalt-catalyzed polybutadienerubbers, such as Taktene® 220 and 221, commercially available fromLANXESS® Corporation; SE BR-1220, commercially available from The DowChemical Company; Europrene® NEOCIS® BR 40 and BR 60, commerciallyavailable from Polimeri Europa®; UBEPOL-BR® rubbers, commerciallyavailable from UBE Industries, Inc.; BR 01, commercially available fromJapan Synthetic Rubber Co., Ltd.; and Neodene high-cisneodymium-catalyzed polybutadiene rubbers, such as Neodene BR 40,commercially available from Karbochem.

Suitable initiator agents include organic peroxides, high energyradiation sources capable of generating free radicals, and combinationsthereof. High energy radiation sources capable of generating freeradicals include, but are not limited to, electron beams, ultra-violetradiation, gamma radiation, X-ray radiation, infrared radiation, heat,and combinations thereof. Suitable organic peroxides include, but arenot limited to, dicumyl peroxide; n-butyl-4,4-di(t-butylperoxy)valerate; 1,1-di(t-butylperoxy)3,3,5-trimethylcyclohexane;2,5-dimethyl-2,5-di(t-butylperoxy) hexane; di-t-butyl peroxide;di-t-amyl peroxide; t-butyl peroxide; t-butyl cumyl peroxide;2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3;di(2-t-butyl-peroxyisopropyl)benzene; dilauroyl peroxide; dibenzoylperoxide; t-butyl hydroperoxide; lauryl peroxide; benzoyl peroxide; andcombinations thereof. Examples of suitable commercially availableperoxides include, but are not limited to Perkadox® BC dicumyl peroxide,commercially available from Akzo Nobel, and Varox® peroxides, such asVarox® ANS benzoyl peroxide and Varox® 2311,1-di(t-butylperoxy)3,3,5-trimethylcyclohexane, commercially availablefrom RT Vanderbilt Company, Inc. Peroxide initiator agents are generallypresent in the rubber composition in an amount of at least 0.05 parts byweight per 100 parts of the base rubber, or an amount within the rangehaving a lower limit of 0.05 parts or 0.1 parts or 0.8 parts or 1 partor 1.25 parts or 1.5 parts by weight per 100 parts of the base rubber,and an upper limit of 2.5 parts or 3 parts or 3.5 parts or 5 parts or 6parts or 10 parts or 15 parts by weight per 100 parts of the baserubber.

Coagents are commonly used with peroxides to increase the state of cure.Suitable coagents include, but are not limited to, metal salts ofunsaturated carboxylic acids; unsaturated vinyl compounds andpolyfunctional monomers (e.g., trimethylolpropane trimethacrylate);phenylene bismaleimide; and combinations thereof. Particular examples ofsuitable metal salts include, but are not limited to, one or more metalsalts of acrylates, diacrylates, methacrylates, and dimethacrylates,wherein the metal is selected from magnesium, calcium, zinc, aluminum,lithium, nickel, and sodium. In a particular embodiment, the coagent isselected from zinc salts of acrylates, diacrylates, methacrylates,dimethacrylates, and mixtures thereof. In another particular embodiment,the coagent is zinc diacrylate. Rubber compositions for forming thecenter of golf balls of the present invention preferably comprise lessthan 40 parts of coagent, by weight per 100 parts of the base rubber. Ina particular embodiment, the coagent is present in the rubbercomposition of the center in an amount of 35 parts or less, or 30 partsor less, or less than 30 parts, or 25 parts or less, or 20 parts orless, by weight per 100 parts of the base rubber, or an amount within arange having a lower limit of 0 or 1 or 5 or 10 parts and an upper limitof 15 or 20 or 25 or 30 or 35 parts, by weight per 100 parts of the baserubber.

When one or more less active coagents are used, such as zincmonomethacrylate and various liquid acrylates and methacrylates, theamount of less active coagent used may be the same as or higher than forzinc diacrylate and zinc dimethacrylate coagents. The desiredcompression may be obtained by adjusting the amount of crosslinking,which can be achieved, for example, by altering the type and amount ofcoagent.

The rubber composition optionally includes a curing agent. Suitablecuring agents include, but are not limited to, sulfur; N-oxydiethylene2-benzothiazole sulfenamide; N,N-di-ortho-tolylguanidine; bismuthdimethyldithiocarbamate; N-cyclohexyl 2-benzothiazole sulfenamide;N,N-diphenylguanidine; 4-morpholinyl-2-benzothiazole disulfide;dipentamethylenethiuram hexasulfide; thiuram disulfides;mercaptobenzothiazoles; sulfenamides; dithiocarbamates; thiuramsulfides; guanidines; thioureas; xanthates; dithiophosphates;aldehyde-amines; dibenzothiazyl disulfide; tetraethylthiuram disulfide;tetrabutylthiuram disulfide; and combinations thereof.

The rubber composition optionally contains one or more antioxidants.Antioxidants are compounds that can inhibit or prevent the oxidativedegradation of the rubber. Some antioxidants also act as free radicalscavengers; thus, when antioxidants are included in the rubbercomposition, the amount of initiator agent used may be as high or higherthan the amounts disclosed herein. Suitable antioxidants include, forexample, dihydroquinoline antioxidants, amine type antioxidants, andphenolic type antioxidants.

The rubber composition may contain one or more fillers to adjust thedensity and/or specific gravity of the core. Exemplary fillers includeprecipitated hydrated silica, clay, talc, asbestos, glass fibers, aramidfibers, mica, calcium metasilicate, zinc sulfate, barium sulfate, zincsulfide, lithopone, silicates, silicon carbide, diatomaceous earth,polyvinyl chloride, carbonates (e.g., calcium carbonate, zinc carbonate,barium carbonate, and magnesium carbonate), metals (e.g., titanium,tungsten, aluminum, bismuth, nickel, molybdenum, iron, lead, copper,boron, cobalt, beryllium, zinc, and tin), metal alloys (e.g., steel,brass, bronze, boron carbide whiskers, and tungsten carbide whiskers),oxides (e.g., zinc oxide, tin oxide, iron oxide, calcium oxide, aluminumoxide, titanium dioxide, magnesium oxide, and zirconium oxide),particulate carbonaceous materials (e.g., graphite, carbon black, cottonflock, natural bitumen, cellulose flock, and leather fiber), metalstearates, microballoons (e.g., glass and ceramic), fly ash, regrind(i.e., core material that is ground and recycled), nanofillers andcombinations thereof. The amount of particulate material(s) present inthe rubber composition is typically within a range having a lower limitof 5 parts or 10 parts by weight per 100 parts of the base rubber, andan upper limit of 30 parts or 50 parts or 100 parts by weight per 100parts of the base rubber. Filler materials may be dual-functionalfillers, such as zinc oxide (which may be used as a filler/acidscavenger) and titanium dioxide (which may be used as afiller/brightener material).

The rubber composition may also contain one or more additives selectedfrom processing aids, processing oils, plasticizers, coloring agents,fluorescent agents, chemical blowing and foaming agents, defoamingagents, stabilizers, softening agents, impact modifiers, free radicalscavengers, accelerators, scorch retarders, and the like. The amount ofadditive(s) typically present in the rubber composition is typicallywithin a range having a lower limit of 0 parts by weight per 100 partsof the base rubber, and an upper limit of 20 parts or 50 parts or 100parts or 150 parts by weight per 100 parts of the base rubber.

The rubber composition optionally includes a soft and fast agent. Asused herein, “soft and fast agent” means any compound or a blend thereofthat is capable of making a core 1) softer (have a lower compression) ata constant COR and/or 2) faster (have a higher COR) at equalcompression, when compared to a core equivalently prepared without asoft and fast agent. Preferably, the rubber composition contains from0.05 phr to 10.0 phr of a soft and fast agent. In one embodiment, thesoft and fast agent is present in an amount within a range having alower limit of 0.05 or 0.1 or 0.2 or 0.5 phr and an upper limit of 1.0or 2.0 or 3.0 or 5.0 phr. In another embodiment, the soft and fast agentis present in an amount of from 2.0 phr to 5.0 phr, or from 2.35 phr to4.0 phr, or from 2.35 phr to 3.0 phr. In an alternative highconcentration embodiment, the soft and fast agent is present in anamount of from 5.0 phr to 10.0 phr, or from 6.0 phr to 9.0 phr, or from7.0 phr to 8.0 phr. In another embodiment, the soft and fast agent ispresent in an amount of 2.6 phr.

Suitable soft and fast agents include, but are not limited to,organosulfur and metal-containing organosulfur compounds; organic sulfurcompounds, including mono, di, and polysulfides, thiol, and mercaptocompounds; inorganic sulfide compounds; blends of an organosulfurcompound and an inorganic sulfide compound; Group VIA compounds;substituted and unsubstituted aromatic organic compounds that do notcontain sulfur or metal; aromatic organometallic compounds;hydroquinones; benzoquinones; quinhydrones; catechols; resorcinols; andcombinations thereof.

As used herein, “organosulfur compound” refers to any compoundcontaining carbon, hydrogen, and sulfur, where the sulfur is directlybonded to at least 1 carbon. As used herein, the term “sulfur compound”means a compound that is elemental sulfur, polymeric sulfur, or acombination thereof. It should be further understood that the term“elemental sulfur” refers to the ring structure of S₈ and that“polymeric sulfur” is a structure including at least one additionalsulfur relative to elemental sulfur.

Particularly suitable as soft and fast agents are organosulfur compoundshaving the following general formula:

where R₁-R₅ can be C₁-C₈ alkyl groups; halogen groups; thiol groups(—SH), carboxylated groups; sulfonated groups; and hydrogen; in anyorder; and also pentafluorothiophenol; 2-fluorothiophenol;3-fluorothiophenol; 4-fluorothiophenol; 2,3-fluorothiophenol;2,4-fluorothiophenol; 3,4-fluorothiophenol; 3,5-fluorothiophenol2,3,4-fluorothiophenol; 3,4,5-fluorothiophenol;2,3,4,5-tetrafluorothiophenol; 2,3,5,6-tetrafluorothiophenol;4-chlorotetrafluorothiophenol; pentachlorothiophenol;2-chlorothiophenol; 3-chlorothiophenol; 4-chlorothiophenol;2,3-chlorothiophenol; 2,4-chlorothiophenol; 3,4-chlorothiophenol;3,5-chlorothiophenol; 2,3,4-chlorothiophenol; 3,4,5-chlorothiophenol;2,3,4,5-tetrachlorothiophenol; 2,3,5,6-tetrachlorothiophenol;pentabromothiophenol; 2-bromothiophenol; 3-bromothiophenol;4-bromothiophenol; 2,3-bromothiophenol; 2,4-bromothiophenol;3,4-bromothiophenol; 3,5-bromothiophenol; 2,3,4-bromothiophenol;3,4,5-bromothiophenol; 2,3,4,5-tetrabromothiophenol;2,3,5,6-tetrabromothiophenol; pentaiodothiophenol; 2-iodothiophenol;3-iodothiophenol; 4-iodothiophenol; 2,3-iodothiophenol;2,4-iodothiophenol; 3,4-iodothiophenol; 3,5-iodothiophenol;2,3,4-iodothiophenol; 3,4,5-iodothiophenol; 2,3,4,5-tetraiodothiophenol;2,3,5,6-tetraiodothiophenoland; zinc salts thereof; non-metal saltsthereof, for example, ammonium salt of pentachlorothiophenol; magnesiumpentachlorothiophenol; cobalt pentachlorothiophenol; and combinationsthereof. Preferably, the halogenated thiophenol compound ispentachlorothiophenol, which is commercially available in neat form orunder the tradename STRUKTOL®, a clay-based carrier containing thesulfur compound pentachlorothiophenol loaded at 45 percent (correlatingto 2.4 parts PCTP). STRUKTOL® is commercially available from StruktolCompany of America of Stow, Ohio. PCTP is commercially available in neatform from eChinachem of San Francisco, Calif. and in the salt form fromeChinachem of San Francisco, Calif. Most preferably, the halogenatedthiophenol compound is the zinc salt of pentachlorothiophenol, which iscommercially available from eChinachem of San Francisco, Calif. Suitableorganosulfur compounds are further disclosed, for example, in U.S. Pat.Nos. 6,635,716, 6,919,393, 7,005,479 and 7,148,279, the entiredisclosures of which are hereby incorporated herein by reference.

Suitable metal-containing organosulfur compounds include, but are notlimited to, cadmium, copper, lead, and tellurium analogs ofdiethyldithiocarbamate, diamyldithiocarbamate, anddimethyldithiocarbamate, and combinations thereof. Additional examplesare disclosed in U.S. Pat. No. 7,005,479, the entire disclosure of whichis hereby incorporated herein by reference.

Suitable disulfides include, but are not limited to, 4,4′-diphenyldisulfide; 4,4′-ditolyl disulfide; 2,2′-benzamido diphenyl disulfide;bis(2-aminophenyl)disulfide; bis(4-aminophenyl)disulfide;bis(3-aminophenyl)disulfide; 2,2′-bis(4-aminonaphthyl)disulfide;2,2′-bis(3-aminonaphthyl)disulfide; 2,2′-bis(4-aminonaphthyl)disulfide;2,2′-bis(5-aminonaphthyl)disulfide; 2,2′-bis(6-aminonaphthyl)disulfide;2,2′-bis(7-aminonaphthyl)disulfide; 2,2′-bis(8-aminonaphthyl)disulfide;1,1′-bis(2-aminonaphthyl)disulfide; 1,1′-bis(3-aminonaphthyl)disulfide;1,1′-bis(3-aminonaphthyl)disulfide; 1,1′-bis(4-aminonaphthyl)disulfide;1,1′-bis(5-aminonaphthyl)disulfide; 1,1′-bis(6-aminonaphthyl)disulfide;1,1′-bis(7-aminonaphthyl)disulfide; 1,1′-bis(8-aminonaphthyl)disulfide;1,2′-diamino-1,2′-dithiodinaphthalene;2,3′-diamino-1,2′-dithiodinaphthalene; bis(4-chlorophenyl)disulfide;bis(2-chlorophenyl)disulfide; bis(3-chlorophenyl)disulfide;bis(4-bromophenyl)disulfide; bis(2-bromophenyl)disulfide;bis(3-bromophenyl)disulfide; bis(4-fluorophenyl)disulfide;bis(4-iodophenyl)disulfide; bis(2,5-dichlorophenyl)disulfide;bis(3,5-dichlorophenyl)disulfide; bis(2,4-dichlorophenyl)disulfide;bis(2,6-dichlorophenyl)disulfide; bis(2,5-dibromophenyl)disulfide;bis(3,5-dibromophenyl)disulfide; bis(2-chloro-5-bromophenyl)disulfide;bis(2,4,6-trichlorophenyl)disulfide;bis(2,3,4,5,6-pentachlorophenyl)disulfide; bis(4-cyanophenyl)disulfide;bis(2-cyanophenyl)disulfide; bis(4-nitrophenyl)disulfide;bis(2-nitrophenyl)disulfide; 2,2′-dithiobenzoic acid ethylester;2,2′-dithiobenzoic acid methylester; 2,2′-dithiobenzoic acid;4,4′-dithiobenzoic acid ethylester; bis(4-acetylphenyl)disulfide;bis(2-acetylphenyl)disulfide; bis(4-formylphenyl)disulfide;bis(4-carbamoylphenyl)disulfide; 1,1′-dinaphthyl disulfide;2,2′-dinaphthyl disulfide; 1,2′-dinaphthyl disulfide;2,2′-bis(1-chlorodinaphthyl)disulfide;2,2′-bis(1-bromonaphthyl)disulfide; 1,1′-bis(2-chloronaphthyl)disulfide;2,2′-bis(1-cyanonaphthyl) disulfide; 2,2′-bis(1-acetylnaphthyl)disulfide; and the like; and combinations thereof.

Suitable inorganic sulfide compounds include, but are not limited to,titanium sulfide, manganese sulfide, and sulfide analogs of iron,calcium, cobalt, molybdenum, tungsten, copper, selenium, yttrium, zinc,tin, and bismuth.

Suitable Group VIA compounds include, but are not limited to, elementalsulfur and polymeric sulfur, such as those which are commerciallyavailable from Elastochem, Inc. of Chardon, Ohio; sulfur catalystcompounds which include PB(RM-S)-80 elemental sulfur and PB(CRST)-65polymeric sulfur, each of which is available from Elastochem, Inc;tellurium catalysts, such as TELLOY®, and selenium catalysts, such asVANDEX®, each of which is commercially available from RT Vanderbilt.

Suitable substituted and unsubstituted aromatic organic components thatdo not include sulfur or a metal include, but are not limited to,4,4′-diphenyl acetylene, azobenzene, and combinations thereof. Thearomatic organic group preferably ranges in size from C₆ to C₂₀, andmore preferably from C₆ to C₁₀.

Suitable substituted and unsubstituted aromatic organometallic compoundsinclude, but are not limited to, those having the formula(R₁)_(x)—R₃-M-R₄—(R₂)_(y), wherein R₁ and R₂ are each hydrogen or asubstituted or unsubstituted C₁₋₂₀ linear, branched, or cyclic alkyl,alkoxy, or alkylthio group, or a single, multiple, or fused ring C₆ toC₂₄ aromatic group; x and y are each an integer from 0 to 5; R₃ and R₄are each selected from a single, multiple, or fused ring C₆ to C₂₄aromatic group; and M includes an azo group or a metal component.Preferably, R₃ and R₄ are each selected from a C₆ to C₁₀ aromatic group,more preferably selected from phenyl, benzyl, naphthyl, benzamido, andbenzothiazyl. Preferably R₁ and R₂ are each selected from substitutedand unsubstituted C₁₋₁₀ linear, branched, and cyclic alkyl, alkoxy, andalkylthio groups, and C₆ to C₁₀ aromatic groups. When R₁, R₂, R₃, and R₄are substituted, the substitution may include one or more of thefollowing substituent groups: hydroxy and metal salts thereof; mercaptoand metal salts thereof; halogen; amino, nitro, cyano, and amido;carboxyl including esters, acids, and metal salts thereof; silyl;acrylates and metal salts thereof; sulfonyl and sulfonamide; andphosphates and phosphites. When M is a metal component, it may be anysuitable elemental metal. The metal is generally a transition metal, andis preferably tellurium or selenium.

Suitable hydroquinones are further disclosed, for example, in U.S.Patent Application Publication No. 2007/0213440, the entire disclosureof which is hereby incorporated herein by reference. Suitablebenzoquinones are further disclosed, for example, in U.S. PatentApplication Publication No. 2007/0213442, the entire disclosure of whichis hereby incorporated herein by reference. Suitable quinhydrones arefurther disclosed, for example, in U.S. Patent Application PublicationNo. 2007/0213441, the entire disclosure of which is hereby incorporatedherein by reference. Suitable catechols and resorcinols are furtherdisclosed, for example, in U.S. Patent Application Publication No.2007/0213144, the entire disclosure of which is hereby incorporatedherein by reference.

In a particular embodiment, the soft and fast agent is selected fromzinc pentachlorothiophenol, pentachlorothiophenol, ditolyl disulfide,diphenyl disulfide, dixylyl disulfide, 2-nitroresorcinol, andcombinations thereof.

Suitable types and amounts of base rubber, initiator agent, coagent,curing agent, filler, and additives are more fully described in, forexample, U.S. Pat. Nos. 6,566,483, 6,695,718, and 6,939,907, 7,041,721and 7,138,460, the entire disclosures of which are hereby incorporatedherein by reference.

The rubber composition of the center optionally includes from 1 to 100phr of a stiffening agent. Suitable stiffening agents include, but arenot limited to, ionomers, acid copolymers and terpolymers, polyamides,and polyesters. Stiffening agents are further disclosed, for example, inU.S. Pat. Nos. 6,120,390 and 6,284,840, the entire disclosures of whichare hereby incorporated herein by reference. A transpolyisoprene (e.g.,TP-301 transpolyisoprene, commercially available from Kuraray Co., Ltd.)or transbutadiene rubber may also be added to increase stiffness to acore layer and/or improve cold-forming properties, which may improveprocessability by making it easier to mold outer core layer half-shellsduring the golf ball manufacturing process. When included in a corelayer composition, the stiffening agent is preferably present in anamount of from 5 to 10 pph.

In another embodiment, the center is formed from a highly neutralizedpolymer composition. Suitable highly neutralized polymer corecompositions are further disclosed, for example, in U.S. Pat. No.7,230,045, the entire disclosure of which is hereby incorporated hereinby reference.

In another embodiment, the center is formed from a first highlyneutralized polymer composition, and the golf ball additionallycomprises a core layer disposed between the center and the intermediatelayer, wherein the core layer disposed between the center and theintermediate layer is formed from a second highly neutralized polymercomposition. Cores having two layers formed from highly neutralizedpolymer compositions are further disclosed, for example, in U.S. Pat.Nos. 7,211,008 and 7,207,903, the entire disclosures of which are herebyincorporated herein by reference.

The intermediate layer is formed from a rubber composition or athermoplastic composition as disclosed below. The intermediate layercomposition preferably has a solid, single core compression of 40 orgreater, or greater than 40, or 50 or greater, or greater than 50, or 60or greater, or greater than 60, or 70 or greater, or greater than 70, or80 or greater, or greater than 80, or 90 or greater, or greater than 90,or 100 or greater, or greater than 100, or a solid, single corecompression within a range having a lower limit of 40 or 50 or 60 or 70or 80 and an upper limit of 95 or 105 or 110 or 120. For purposes of thepresent disclosure, “solid, single core compression” refers to thecompression of a 1.550 inch solid sphere formed from the composition.

Suitable rubber compositions for forming the intermediate layer includethose disclosed above as suitable for forming the center, except thatrubber compositions for forming the intermediate layer preferablycomprise 35 parts or greater, or greater than 35 parts, or 40 parts orgreater, or greater than 40 parts, or 45 parts or greater, or greaterthan 45 parts, or 50 parts or greater, or greater than 50 parts, or 55parts or greater, or greater than 55 parts, or 60 parts or greater, orgreater than 60 parts, of the coagent, by weight per 100 parts of thebase rubber.

Suitable thermoplastic compositions for forming the intermediate layerinclude partially- and fully-neutralized ionomers optionally blendedwith a maleic anhydride-grafted non-ionomeric polymer, graft copolymersof ionomer and polyamide, and the following non-ionomeric polymers,including homopolymers and copolymers thereof, as well as theirderivatives that are compatibilized with at least one grafted orcopolymerized functional group, such as maleic anhydride, amine, epoxy,isocyanate, hydroxyl, sulfonate, phosphonate, and the like:

-   -   (a) polyesters, particularly those modified with a        compatibilizing group such as sulfonate or phosphonate,        including modified poly(ethylene terephthalate), modified        poly(butylene terephthalate), modified poly(propylene        terephthalate), modified poly(trimethylene terephthalate),        modified poly(ethylene naphthenate), and those disclosed in U.S.        Pat. Nos. 6,353,050, 6,274,298, and 6,001,930, the entire        disclosures of which are hereby incorporated herein by        reference, and blends of two or more thereof;    -   (b) polyamides, polyamide-ethers, and polyamide-esters, and        those disclosed in U.S. Pat. Nos. 6,187,864, 6,001,930, and        5,981,654, the entire disclosures of which are hereby        incorporated herein by reference, and blends of two or more        thereof;    -   (c) polyurethanes, polyureas, polyurethane-polyurea hybrids, and        blends of two or more thereof;    -   (d) fluoropolymers, such as those disclosed in U.S. Pat. Nos.        5,691,066, 6,747,110 and 7,009,002, the entire disclosures of        which are hereby incorporated herein by reference, and blends of        two or more thereof;    -   (e) non-ionomeric acid polymers, such as E/Y— and E/X/Y-type        copolymers, wherein E is an olefin (e.g., ethylene), Y is a        carboxylic acid such as acrylic, methacrylic, crotonic, maleic,        fumaric, or itaconic acid, and X is a softening comonomer such        as vinyl esters of aliphatic carboxylic acids wherein the acid        has from 2 to 10 carbons, alkyl ethers wherein the alkyl group        has from 1 to 10 carbons, and alkyl alkylacrylates such as alkyl        methacrylates wherein the alkyl group has from 1 to 10 carbons;        and blends of two or more thereof;    -   (f) metallocene-catalyzed polymers, such as those disclosed in        U.S. Pat. Nos. 6,274,669, 5,919,862, 5,981,654, and 5,703,166,        the entire disclosures of which are hereby incorporated herein        by reference, and blends of two or more thereof;    -   (g) polystyrenes, such as poly(styrene-co-maleic anhydride),        acrylonitrile-butadiene-styrene, poly(styrene sulfonate),        polyethylene styrene, and blends of two or more thereof;    -   (h) polypropylenes and polyethylenes, particularly grafted        polypropylene and grafted polyethylenes that are modified with a        functional group, such as maleic anhydride, and blends of two or        more thereof;    -   (i) polyvinyl chlorides and grafted polyvinyl chlorides, and        blends of two or more thereof;    -   (j) polyvinyl acetates, preferably having less than about 9% of        vinyl acetate by weight, and blends of two or more thereof;    -   (k) polycarbonates, blends of        polycarbonate/acrylonitrile-butadiene-styrene, blends of        polycarbonate/polyurethane, blends of polycarbonate/polyester,        and blends of two or more thereof;    -   (l) polyvinyl alcohols, and blends of two or more thereof;    -   (m) polyethers, such as polyarylene ethers, polyphenylene        oxides, block copolymers of alkenyl aromatics with vinyl        aromatics and poly(amic ester)s, and blends of two or more        thereof;

(n) polyimides, polyetherketones, polyamideimides, and blends of two ormore thereof;

(o) polycarbonate/polyester copolymers and blends; and

(p) combinations of any two or more of the above thermoplastic polymers.

Ionomer compositions suitable for forming the intermediate layercomprise one or more acid polymers, each of which is partially- orfully-neutralized, and optionally additives, fillers, and/or melt flowmodifiers. Suitable acid polymers are salts of homopolymers andcopolymers of α,β-ethylenically unsaturated mono- or dicarboxylic acids,and combinations thereof, optionally including a softening monomer, andpreferably having an acid content (prior to neutralization) of from 1 wt% to 30 wt %, more preferably from 5 wt % to 20 wt %. The acid polymeris preferably neutralized to 70% or higher, including up to 100%, with asuitable cation source, such as metal cations and salts thereof, organicamine compounds, ammonium, and combinations thereof. Preferred cationsources are metal cations and salts thereof, wherein the metal ispreferably lithium, sodium, potassium, magnesium, calcium, barium, lead,tin, zinc, aluminum, manganese, nickel, chromium, copper, or acombination thereof. Suitable additives and fillers include, forexample, blowing and foaming agents, optical brighteners, coloringagents, fluorescent agents, whitening agents, UV absorbers, lightstabilizers, defoaming agents, processing aids, mica, talc, nanofillers,antioxidants, stabilizers, softening agents, fragrance components,plasticizers, impact modifiers, acid copolymer wax, surfactants;inorganic fillers, such as zinc oxide, titanium dioxide, tin oxide,calcium oxide, magnesium oxide, barium sulfate, zinc sulfate, calciumcarbonate, zinc carbonate, barium carbonate, mica, talc, clay, silica,lead silicate, and the like; high specific gravity metal powder fillers,such as tungsten powder, molybdenum powder, and the like; regrind, i.e.,core material that is ground and recycled; and nano-fillers. Suitablemelt flow modifiers include, for example, fatty acids and salts thereof,polyamides, polyesters, polyacrylates, polyurethanes, polyethers,polyureas, polyhydric alcohols, and combinations thereof. Suitableionomer compositions include blends of highly neutralized polymers(i.e., neutralized to 70% or higher) with partially neutralized ionomersas disclosed, for example, in U.S. Patent Application Publication No.2006/0128904, the entire disclosure of which is hereby incorporatedherein by reference. Suitable ionomer compositions also include blendsof one or more partially- or fully-neutralized polymers with additionalthermoplastic and thermoset materials, including, but not limited to,non-ionomeric acid copolymers, engineering thermoplastics, fattyacid/salt-based highly neutralized polymers, polybutadienes,polyurethanes, polyureas, polyesters, polycarbonate/polyester blends,thermoplastic elastomers, maleic anhydride-grafted metallocene-catalyzedpolymers, and other conventional polymeric materials. Suitable ionomercompositions are further disclosed, for example, in U.S. Pat. Nos.6,653,382, 6,756,436, 6,777,472, 6,894,098, 6,919,393, and 6,953,820,and U.S. Patent Application Publication No. 2006/0106175, the entiredisclosures of which are hereby incorporated herein by reference.

Examples of commercially available thermoplastics suitable for formingthe intermediate layer include, but are not limited to, Pebax®thermoplastic polyether block amides, commercially available from ArkemaInc.; Surlyn® ionomer resins, Hytrel® thermoplastic polyesterelastomers, and ionomer materials sold under the trade names DuPont® HPF1000 and HPF 2000, all of which are commercially available from E. I. duPont de Nemours and Company; Iotek® ionomers, commercially availablefrom ExxonMobil Chemical Company; Amplify® IO ionomers of ethyleneacrylic acid copolymers, commercially available from The Dow ChemicalCompany; Clarix® ionomer resins, commercially available from A. SchulmanInc.; Elastollan® polyurethane-based thermoplastic elastomers,commercially available from BASF; and Xylex® polycarbonate/polyesterblends, commercially available from SABIC Innovative Plastics.

In a particular embodiment, the intermediate layer is formed from acomposition selected from polybutadienes, ionomers,metallocene-catalyzed polyolefins, polyether esters, polyether amides,maleic anhydride-grafted non-ionomeric polymers, polyurethanes,polyureas, copolymers and blends of polyurethane and polyurea, andethylene propylene diene rubber. In a particular aspect of thisembodiment, the intermediate layer is formed from a polybutadienecomposition, preferably comprising greater than 50 phr of a coagentselected from the group consisting of metal salts of diacrylates,dimethacrylates, and monomethacrylates. In another particular aspect ofthis embodiment, the intermediate layer composition has a flexuralmodulus of 20,000 psi or greater, or greater than 20,000 psi, or 40,000psi or greater, or greater than 40,000 psi, or 50,000 or greater, orgreater than 50,000 psi, or a flexural modulus within a range having alower limit of 25,000 or 40,000 or 50,000 or 60,000 psi and an upperlimit of 90,000 or 100,000 or 120,000 psi.

Intermediate layer compositions may include a stiffening agent. Suitablestiffening agents include those disclosed above for use in the centercomposition. Preferably, if present, a stiffening agent is present inthe intermediate layer and not in the center.

Intermediate layer compositions may include high levels of filler,fiber, or flake. The specific gravity of the intermediate layer ispreferably greater than equal to that of the center.

Golf balls of the present invention include a cover having one or morelayers. Suitable cover materials include, but are not limited to,ionomer resins and blends thereof (e.g., Surlyn® ionomer resins andDuPont® HPF 1000 and HPF 2000, commercially available from E. I. du Pontde Nemours and Company; Iotek® ionomers, commercially available fromExxonMobil Chemical Company; Amplify® 10 ionomers of ethylene acrylicacid copolymers, commercially available from The Dow Chemical Company;and Clarix® ionomer resins, commercially available from A. SchulmanInc.); polyurethanes; polyureas; copolymers and blends of polyurethaneand polyurea; polyethylene, including, for example, low densitypolyethylene, linear low density polyethylene, and high densitypolyethylene; polypropylene; rubber-toughened olefin polymers; acidcopolymers, e.g., (meth)acrylic acid, which do not become part of anionomeric copolymer; plastomers; flexomers; styrene/butadiene/styreneblock copolymers; styrene/ethylene-butylene/styrene block copolymers;dynamically vulcanized elastomers; ethylene vinyl acetates; ethylenemethyl acrylates; polyvinyl chloride resins; polyamides, amide-esterelastomers, and graft copolymers of ionomer and polyamide, including,for example, Pebax® thermoplastic polyether block amides, commerciallyavailable from Arkema Inc; crosslinked trans-polyisoprene and blendsthereof; polyester-based thermoplastic elastomers, such as Hytrel®,commercially available from E. I. du Pont de Nemours and Company;polyurethane-based thermoplastic elastomers, such as Elastollan®,commercially available from BASF; synthetic or natural vulcanizedrubber; and combinations thereof.

Compositions comprising an ionomer or a blend of two or more ionomersare particularly suitable cover materials. Preferred ionomer covercompositions include, but are not limited to:

-   -   (a) a composition comprising a “high acid ionomer” (i.e., having        an acid content of greater than 16 wt %), such as Surlyn 8150®;    -   (b) a composition comprising a high acid ionomer and a maleic        anhydride-grafted non-ionomeric polymer (e.g., Fusabond®        functionalized polymers). A particularly preferred blend of high        acid ionomer and maleic anhydride-grafted polymer is a 84 wt        %/16 wt % blend of Surlyn 8150® and Fusabond®. Blends of high        acid ionomers with maleic anhydride-grafted polymers are further        disclosed, for example, in U.S. Pat. Nos. 6,992,135 and        6,677,401, the entire disclosures of which are hereby        incorporated herein by reference;    -   (c) a composition comprising a 50/45/5 blend of Surlyn®        8940/Surlyn® 9650/Nucrel® 960, preferably having a material        hardness of from 80 to 85 Shore C;    -   (d) a composition comprising a 50/25/25 blend of Surlyn®        8940/Surlyn® 9650/Surlyn® 9910, preferably having a material        hardness of about 90 Shore C;    -   (e) a composition comprising a 50/50 blend of Surlyn®        8940/Surlyn® 9650, preferably having a material hardness of        about 86 Shore C;    -   (f) a composition comprising a blend of Surlyn® 7940/Surlyn®        8940, optionally including a melt flow modifier;    -   (g) a composition comprising a blend of a first high acid        ionomer and a second high acid ionomer, wherein the first high        acid ionomer is neutralized with a different cation than the        second high acid ionomer (e.g., 50/50 blend of Surlyn® 8150 and        Surlyn® 9150), optionally including one or more melt flow        modifiers such as an ionomer, ethylene-acid copolymer or ester        terpolymer; and    -   (h) a composition comprising a blend of a first high acid        ionomer and a second high acid ionomer, wherein the first high        acid ionomer is neutralized with a different cation than the        second high acid ionomer, and from 0 to 10 wt % of an        ethylene/acid/ester ionomer wherein the ethylene/acid/ester        ionomer is neutralized with the same cation as either the first        high acid ionomer or the second high acid ionomer or a different        cation than the first and second high acid ionomers (e.g., a        blend of 40-50 wt % Surlyn® 8140, 40-50 wt % Surlyn® 9120, and        0-10 wt % Surlyn® 6320).

Surlyn 8150®, Surlyn® 8940, and Surlyn® 8140 are different grades ofE/MAA copolymer in which the acid groups have been partially neutralizedwith sodium ions. Surlyn® 9650, Surlyn® 9910, Surlyn® 9150, and Surlyn®9120 are different grades of E/MAA copolymer in which the acid groupshave been partially neutralized with zinc ions. Surlyn® 7940 is an E/MAAcopolymer in which the acid groups have been partially neutralized withlithium ions. Surlyn® 6320 is a very low modulus magnesium ionomer witha medium acid content. Nucrel® 960 is an E/MAA copolymer resin nominallymade with 15 wt % methacrylic acid. Surlyn® ionomers, Fusabond®polymers, and Nucrel® copolymers are commercially available from E. I.du Pont de Nemours and Company.

Ionomer cover compositions can be blended with non-ionic thermoplasticresins, particularly to manipulate product properties. Examples ofsuitable non-ionic thermoplastic resins include, but are not limited to,polyurethane, poly-ether-ester, poly-amide-ether, polyether-urea,thermoplastic polyether block amides (e.g., Pebax® block copolymers,commercially available from Arkema Inc.), styrene-butadiene-styreneblock copolymers, styrene(ethylene-butylene)-styrene block copolymers,polyamides, polyesters, polyolefins (e.g., polyethylene, polypropylene,ethylene-propylene copolymers, polyethylene-(meth)acrylate,plyethylene-(meth)acrylic acid, functionalized polymers with maleicanhydride grafting, Fusabond® functionalized polymers commerciallyavailable from E. I. du Pont de Nemours and Company, functionalizedpolymers with epoxidation, elastomers (e.g., ethylene propylene dienemonomer rubber, metallocene-catalyzed polyolefin) and ground powders ofthermoset elastomers.

Suitable ionomer cover materials are further disclosed, for example, inU.S. Pat. Nos. 6,653,382, 6,756,436, 6,894,098, 6,919,393, and6,953,820, the entire disclosures of which are hereby incorporated byreference.

Polyurethanes, polyureas, and blends and hybrids ofpolyurethane/polyurea are also particularly suitable for forming coverlayers. When used as cover layer materials, polyurethanes and polyureascan be thermoset or thermoplastic. Thermoset materials can be formedinto golf ball layers by conventional casting or reaction injectionmolding techniques. Thermoplastic materials can be formed into golf balllayers by conventional compression or injection molding techniques.

Polyurethane cover compositions of the present invention include thoseformed from the reaction product of at least one polyisocyanate and atleast one curing agent. The curing agent can include, for example, oneor more diamines, one or more polyols, or a combination thereof. The atleast one polyisocyanate can be combined with one or more polyols toform a prepolymer, which is then combined with the at least one curingagent. Thus, when polyols are described herein they may be suitable foruse in one or both components of the polyurethane material, i.e., aspart of a prepolymer and in the curing agent. The curing agent includesa polyol curing agent preferably selected from the group consisting ofethylene glycol; diethylene glycol; polyethylene glycol; propyleneglycol; polypropylene glycol; lower molecular weight polytetramethyleneether glycol; 1,3-bis(2-hydroxyethoxy)benzene;1,3-bis-[2-(2-hydroxyethoxy)ethoxy]benzene;1,3-bis-{2-[2-(2-hydroxyethoxy)ethoxy]ethoxy}benzene; 1,4-butanediol;1,5-pentanediol; 1,6-hexanediol; resorcinol-di-(β-hydroxyethyl)ether;hydroquinone-di-(β-hydroxyethyl)ether; trimethylol propane; andcombinations thereof.

Suitable polyurethane cover compositions of the present invention alsoinclude those formed from the reaction product of at least oneisocyanate and at least one curing agent or the reaction produce of atleast one isocyanate, at least one polyol, and at least one curingagent. Preferred isocyanates include those selected from the groupconsisting of 4,4′-diphenylmethane diisocyanate, polymeric4,4′-diphenylmethane diisocyanate, carbodiimide-modified liquid4,4′-diphenylmethane diisocyanate, 4,4′-dicyclohexylmethanediisocyanate, p-phenylene diisocyanate, toluene diisocyanate,isophoronediisocyanate, p-methylxylene diisocyanate, m-methylxylenediisocyanate, o-methylxylene diisocyanate, and combinations thereof.Preferred polyols include those selected from the group consisting ofpolyether polyol, hydroxy-terminated polybutadiene, polyester polyol,polycaprolactone polyol, polycarbonate polyol, and combinations thereof.Preferred curing agents include polyamine curing agents, polyol curingagents, and combinations thereof. Polyamine curing agents areparticularly preferred. Preferred polyamine curing agents include, forexample, 3,5-dimethylthio-2,4-toluenediamine, or an isomer thereof;3,5-diethyltoluene-2,4-diamine, or an isomer thereof;4,4′-bis-(sec-butylamino)-diphenylmethane;1,4-bis-(sec-butylamino)-benzene, 4,4′-methylene-bis-(2-chloroaniline);4,4′-methylene-bis-(3-chloro-2,6-diethylaniline); trimethyleneglycol-di-p-aminobenzoate; polytetramethyleneoxide-di-p-aminobenzoate;N,N′-dialkyldiamino diphenyl methane; p,p′-methylene dianiline;phenylenediamine; 4,4′-methylene-bis-(2-chloroaniline);4,4′-methylene-bis-(2,6-diethylaniline);4,4′-diamino-3,3′-diethyl-5,5′-dimethyl diphenylmethane; 2,2′,3,3′-tetrachloro diamino diphenylmethane;4,4′-methylene-bis-(3-chloro-2,6-diethylaniline); and combinationsthereof.

The present invention is not limited by the use of a particularpolyisocyanate in the cover composition. Suitable polyisocyanatesinclude, but are not limited to, 4,4′-diphenylmethane diisocyanate(“MDI”), polymeric MDI, carbodiimide-modified liquid MDI,4,4′-dicyclohexylmethane diisocyanate (“H₁₂MDI”), p-phenylenediisocyanate (“PPDI”), toluene diisocyanate (“TDI”),3,3′-dimethyl-4,4′-biphenylene diisocyanate (“TODI”),isophoronediisocyanate (“IPDI”), hexamethylene diisocyanate (“HDI”),naphthalene diisocyanate (“NDI”); xylene diisocyanate (“XDI”);para-tetramethylxylene diisocyanate (“p-TMXDI”); meta-tetramethylxylenediisocyanate (“m-TMXDI”); ethylene diisocyanate;propylene-1,2-diisocyanate; tetramethylene-1,4-diisocyanate; cyclohexyldiisocyanate; 1,6-hexamethylene-diisocyanate (“HDI”);dodecane-1,12-diisocyanate; cyclobutane-1,3-diisocyanate;cyclohexane-1,3-diisocyanate; cyclohexane-1,4-diisocyanate;1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane; methylcyclohexylene diisocyanate; triisocyanate of HDI; triisocyanate of2,4,4-trimethyl-1,6-hexane diisocyanate (“TMDI”), tetracenediisocyanate, naphthalene diisocyanate, anthracene diisocyanate; andcombinations thereof. Polyisocyanates are known to those of ordinaryskill in the art as having more than one isocyanate group, e.g., di-,tri-, and tetra-isocyanate. Preferably, the polyisocyanate is selectedfrom MDI, PPDI, TDI, and combinations thereof. More preferably, thepolyisocyanate includes MDI. It should be understood that, as usedherein, the term “MDI” includes 4,4′-diphenylmethane diisocyanate,polymeric MDI, carbodiimide-modified liquid MDI, combinations thereofand, additionally, that the diisocyanate employed may be “low freemonomer,” understood by one of ordinary skill in the art to have lowerlevels of “free” monomer isocyanate groups than conventionaldiisocyanates, i.e., the compositions of the invention typically haveless than about 0.1% free monomer groups. Examples of “low free monomer”diisocyanates include, but are not limited to Low Free Monomer MDI, LowFree Monomer TDI, and Low Free Monomer PPDI.

The at least one polyisocyanate should have less than 14% unreacted NCOgroups. Preferably, the at least one polyisocyanate has no greater than8.5% NCO, more preferably from 2.5% to 8.0%, even more preferably from4.0% to 7.2%, and most preferably from 5.0% to 6.5%.

The present invention is not limited by the use of a particular polyolin the cover composition. In one embodiment, the molecular weight of thepolyol is from about 200 to about 6000. Exemplary polyols include, butare not limited to, polyether polyols, hydroxy-terminated polybutadiene(including partially/fully hydrogenated derivatives), polyester polyols,polycaprolactone polyols, and polycarbonate polyols. Particularlypreferred are polytetramethylene ether glycol (“PTMEG”), polyethylenepropylene glycol, polyoxypropylene glycol, and combinations thereof. Thehydrocarbon chain can have saturated or unsaturated bonds andsubstituted or unsubstituted aromatic and cyclic groups. Preferably, thepolyol of the present invention includes PTMEG. Suitable polyesterpolyols include, but are not limited to, polyethylene adipate glycol,polybutylene adipate glycol, polyethylene propylene adipate glycol,ortho-phthalate-1,6-hexanediol, and combinations thereof. Thehydrocarbon chain can have saturated or unsaturated bonds, orsubstituted or unsubstituted aromatic and cyclic groups. Suitablepolycaprolactone polyols include, but are not limited to,1,6-hexanediol-initiated polycaprolactone, diethylene glycol initiatedpolycaprolactone, trimethylol propane initiated polycaprolactone,neopentyl glycol initiated polycaprolactone, 1,4-butanediol-initiatedpolycaprolactone, and combinations thereof. The hydrocarbon chain canhave saturated or unsaturated bonds, or substituted or unsubstitutedaromatic and cyclic groups. Suitable polycarbonates include, but are notlimited to, polyphthalate carbonate. The hydrocarbon chain can havesaturated or unsaturated bonds, or substituted or unsubstituted aromaticand cyclic groups.

Polyamine curatives are also suitable for use in the curing agent ofpolyurethane compositions and have been found to improve cut, shear, andimpact resistance of the resultant balls. Preferred polyamine curativesinclude, but are not limited to, 3,5-dimethylthio-2,4-toluenediamine andisomers thereof; 3,5-diethyltoluene-2,4-diamine and isomers thereof,such as 3,5-diethyltoluene-2,6-diamine;4,4′-bis-(sec-butylamino)-diphenylmethane;1,4-bis-(sec-butylamino)-benzene, 4,4′-methylene-bis-(2-chloroaniline);4,4′-methylene-bis-(3-chloro-2,6-diethylaniline);polytetramethyleneoxide-di-p-aminobenzoate; N,N′-dialkyldiamino diphenylmethane; p,p′-methylene dianiline (“MDA”); m-phenylenediamine (“MPDA”);4,4′-methylene-bis-(2-chloroaniline) (“MOCA”);4,4′-methylene-bis-(2,6-diethylaniline);4,4′-diamino-3,3′-diethyl-5,5′-dimethyl diphenylmethane; 2,2′,3,3′-tetrachloro diamino diphenylmethane;4,4′-methylene-bis-(3-chloro-2,6-diethylaniline); trimethylene glycoldi-p-aminobenzoate; and combinations thereof. Preferably, the curingagent of the present invention includes3,5-dimethylthio-2,4-toluenediamine and isomers thereof, such asETHACURE 300. Suitable polyamine curatives, which include both primaryand secondary amines, preferably have weight average molecular weightsranging from about 64 to about 2000.

At least one of a diol, triol, tetraol, or hydroxy-terminated curativemay be added to the polyurethane composition. Suitable diol, triol, andtetraol groups include ethylene glycol; diethylene glycol; polyethyleneglycol; propylene glycol; polypropylene glycol; lower molecular weightpolytetramethylene ether glycol; 1,3-bis(2-hydroxyethoxy)benzene;1,3-bis-[2-(2-hydroxyethoxy)ethoxy]benzene;1,3-bis-{2-[2-(2-hydroxyethoxy)ethoxy]ethoxy}benzene; 1,4-butanediol;1,5-pentanediol; 1,6-hexanediol; resorcinol-di-(4-hydroxyethyl)ether;hydroquinone-di-(4-hydroxyethyl)ether; and combinations thereof.Preferred hydroxy-terminated curatives include ethylene glycol;diethylene glycol; 1,4-butanediol; 1,5-pentanediol; 1,6-hexanediol,trimethylol propane, and combinations thereof. Preferably, thehydroxy-terminated curative has a molecular weights ranging from about48 to 2000. It should be understood that molecular weight, as usedherein, is the absolute weight average molecular weight and would beunderstood as such by one of ordinary skill in the art.

Both the hydroxy-terminated and amine curatives can include one or moresaturated, unsaturated, aromatic, and cyclic groups. Additionally, thehydroxy-terminated and amine curatives can include one or more halogengroups. The polyurethane composition can be formed with a blend ormixture of curing agents. If desired, however, the polyurethanecomposition may be formed with a single curing agent.

Any method known to one of ordinary skill in the art may be used tocombine the polyisocyanate, polyol, and curing agent of the presentinvention. One commonly employed method, known in the art as a one-shotmethod, involves concurrent mixing of the polyisocyanate, polyol, andcuring agent. This method results in a mixture that is inhomogeneous(more random) and affords the manufacturer less control over themolecular structure of the resultant composition. A preferred method ofmixing is known as a prepolymer method. In this method, thepolyisocyanate and the polyol are mixed separately prior to addition ofthe curing agent. This method affords a more homogeneous mixtureresulting in a more consistent polymer composition.

Suitable polyurethanes are further disclosed, for example, in U.S. Pat.Nos. 5,334,673, 6,506,851, 6,756,436, 6,867,279, 6,960,630, and7,105,623, the entire disclosures of which are hereby incorporatedherein by reference. Suitable polyureas are further disclosed, forexample, in U.S. Pat. Nos. 5,484,870 and 6,835,794, and U.S. PatentApplication No. 60/401,047, the entire disclosures of which are herebyincorporated herein by reference, and also include dual-curing polyureasas disclosed, for example, in U.S. patent application Ser. No.12/122,406 filed on May 16, 2008; Ser. No. 12/122,333, filed on May 16,2008; Ser. No. 12/122,370, filed on May 16, 2008; Ser. No. 12/122,384,filed on May 16, 2008; and Ser. No. 12/122,396, filed on May 16, 2008,the entire disclosures of which are hereby incorporated herein byreference. Suitable polyurethane-urea cover materials includepolyurethane/polyurea blends and copolymers comprising urethane and ureasegments, as disclosed in U.S. Patent Application Publication No.2007/0117923, the entire disclosure of which is hereby incorporatedherein by reference.

Golf ball cover compositions may include a flow modifier, such as, butnot limited to, Nucrel® acid copolymer resins, and particularly Nucrel®960. Nucrel® acid copolymer resins are commercially available from E. I.du Pont de Nemours and Company.

Cover compositions may also include one or more filler(s), such as thefillers given above for rubber compositions of the present invention(e.g., titanium dioxide, barium sulfate, etc.), and/or additive(s), suchas coloring agents, fluorescent agents, whitening agents, antioxidants,dispersants, UV absorbers, light stabilizers, plasticizers, surfactants,compatibility agents, foaming agents, reinforcing agents, releaseagents, and the like.

Suitable cover materials and constructions also include, but are notlimited to, those disclosed in U.S. Patent Application Publication No.2005/0164810, U.S. Pat. Nos. 5,919,100, 6,117,025, 6,767,940, and6,960,630, and PCT Publications WO00/23519 and WO00/29129, the entiredisclosures of which are hereby incorporated herein by reference.

In a particular embodiment, the cover consists of an outer cover layerformed from a composition selected from ionomers, metallocene-catalyzedpolyolefins, maleic anhydride-grafted non-ionomeric polymers (e.g.,Fusabond® functionalized polymers), polyurethanes, polyureas, copolymersand blends of polyurethane and polyurea, polyether amides, polyesters,polybutadiene rubber, ethylene propylene diene rubber, and combinationsthereof. In a particular aspect of this embodiment, the outer coverlayer composition has a flexural modulus of 60,000 psi or less, or lessthan 60,000 psi, or 50,000 psi or less, or less than 50,000 psi, or40,000 psi or less, or less than 40,000 psi. In another particularaspect of this embodiment, the outer cover layer composition has amaterial hardness equal to or less than that of the intermediate layercomposition.

For purposes of the present disclosure, material hardness is measuredaccording to ASTM D2240 and generally involves measuring the hardness ofa flat “slab” or “button” formed of the material. It should beunderstood that there is a fundamental difference between “materialhardness” and “hardness as measured directly on a golf ball.” Hardnessas measured directly on a golf ball (or other spherical surface)typically results in a different hardness value than material hardness.This difference in hardness values is due to several factors including,but not limited to, ball construction (i.e., core type, number of coreand/or cover layers, etc.), ball (or sphere) diameter, and the materialcomposition of adjacent layers. It should also be understood that thetwo measurement techniques are not linearly related and, therefore, onehardness value cannot easily be correlated to the other. Unless statedotherwise, the hardness values given herein for cover materials arematerial hardness values measured according to ASTM D2240, with allvalues reported following 10 days of aging at 50% relative humidity and23° C.

A moisture vapor barrier layer is optionally employed between the coreand the cover. Moisture vapor barrier layers are further disclosed, forexample, in U.S. Pat. Nos. 6,632,147, 6,838,028, 6,932,720, 7,004,854,and 7,182,702, and U.S. Patent Application Publication Nos.2003/0069082, 2003/0069085, 2003/0130062, 2004/0147344, 2004/0185963,2006/0068938, 2006/0128505 and 2007/0129172, the entire disclosures ofwhich are hereby incorporated herein by reference.

In addition to the material disclosed above, any of the core or coverlayers may comprise one or more of the following materials:thermoplastic elastomer, thermoset elastomer, synthetic rubber,thermoplastic vulcanizate, copolymeric ionomer, terpolymeric inomer,polycarbonate, polyolefin, polyamide, copolymeric polyamide, polyesters,polyester-amides, polyether-amides, polyvinyl alcohols,acrylonitrile-butadiene-styrene copolymers, polyarylate, polyacrylate,polyphenylene ether, impact-modified polyphenylene ether, high impactpolystyrene, diallyl phthalate polymer, metallocene-catalyzed polymers,styrene-acrylonitrile (SAN), olefin-modified SAN,acrylonitrile-styrene-acrylonitrile, styrene-maleic anhydride (S/MA)polymer, styrenic copolymer, functionalized styrenic copolymer,functionalized styrenic terpolymer, styrenic terpolymer, cellulosepolymer, liquid crystal polymer (LCP), ethylene-propylene-diene rubber(EPDM), ethylene-vinyl acetate copolymer (EVA), ethylene propylenerubber (EPR), ethylene vinyl acetate, polyurea, and polysiloxane.Suitable polyamides for use as an additional material in compositionsdisclosed herein also include resins obtained by: (1) polycondensationof (a) a dicarboxylic acid, such as oxalic acid, adipic acid, sebacicacid, terephthalic acid, isophthalic acid or 1,4-cyclohexanedicarboxylicacid, with (b) a diamine, such as ethylenediamine,tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, ordecamethylenediamine, 1,4-cyclohexyldiamine or m-xylylenediamine; (2) aring-opening polymerization of cyclic lactam, such as ε-caprolactam orω-laurolactam; (3) polycondensation of an aminocarboxylic acid, such as6-aminocaproic acid, 9-aminononanoic acid, 11-aminoundecanoic acid or12-aminododecanoic acid; or (4) copolymerzation of a cyclic lactam witha dicarboxylic acid and a diamine. Specific examples of suitablepolyamides include Nylon 6, Nylon 66, Nylon 610, Nylon 11, Nylon 12,copolymerized Nylon, Nylon MXD6, and Nylon 46.

Other preferred materials suitable for use as an additional material ingolf ball compositions disclosed herein include Skypel polyesterelastomers, commercially available from SK Chemicals of South Korea;Septon® diblock and triblock copolymers, commercially available fromKuraray Corporation of Kurashiki, Japan; and Kraton® diblock andtriblock copolymers, commercially available from Kraton Polymers LLC ofHouston, Tex.

Ionomer compositions used to form golf ball layers of the presentinvention can be blended with non-ionic thermoplastic resins,particularly to manipulate product properties. Examples of suitablenon-ionic thermoplastic resins include, but are not limited to,polyurethane, poly-ether-ester, poly-amide-ether, polyether-urea, Pebax®thermoplastic polyether block amides commercially available from ArkemaInc., styrene-butadiene-styrene block copolymers,styrene(ethylene-butylene)-styrene block copolymers, polyamides,polyesters, polyolefins (e.g., polyethylene, polypropylene,ethylene-propylene copolymers, ethylene-(meth)acrylate,ethylene-(meth)acrylic acid, functionalized polymers with maleicanhydride grafting, epoxidation, etc., elastomers (e.g., EPDM,metallocene-catalyzed polyethylene) and ground powders of the thermosetelastomers.

Compositions disclosed herein can be either foamed or filled withdensity adjusting materials to provide desirable golf ball performancecharacteristics.

The present invention is not limited by any particular process forforming the golf ball layer(s). It should be understood that thelayer(s) can be formed by any suitable technique, including injectionmolding, compression molding, casting, and reaction injection molding.

When injection molding is used, the composition is typically in apelletized or granulated form that can be easily fed into the throat ofan injection molding machine wherein it is melted and conveyed via ascrew in a heated barrel at temperatures of from 150° F. to 600° F.,preferably from 200° F. to 500° F. The molten composition is ultimatelyinjected into a closed mold cavity, which may be cooled, at ambient orat an elevated temperature, but typically the mold is cooled to atemperature of from 50° F. to 70° F. After residing in the closed moldfor a time of from 1 second to 300 seconds, preferably from 20 secondsto 120 seconds, the core and/or core plus one or more additional core orcover layers is removed from the mold and either allowed to cool atambient or reduced temperatures or is placed in a cooling fluid such aswater, ice water, dry ice in a solvent, or the like.

When compression molding is used to form a core, the composition isfirst formed into a preform or slug of material, typically in acylindrical or roughly spherical shape at a weight slightly greater thanthe desired weight of the molded core. Prior to this step, thecomposition may be first extruded or otherwise melted and forced througha die after which it is cut into a cylindrical preform. The preform isthen placed into a compression mold cavity and compressed at a moldtemperature of from 150° F. to 400° F., preferably from 250° F. to 400°F., and more preferably from 300° F. to 400° F. When compression moldinga cover layer, half-shells of the cover layer material are first formedvia injection molding. A core is then enclosed within two half-shells,which is then placed into a compression mold cavity and compressed.

Reaction injection molding processes are further disclosed, for example,in U.S. Pat. Nos. 6,083,119, 7,208,562, 7,281,997, 7,282,169, 7,338,391,and U.S. Patent Application Publication No. 2006/0247073, the entiredisclosures of which are hereby incorporated herein by reference.

Thermoplastic layers herein may be treated in such a manner as to createa positive or negative hardness gradient. In golf ball layers of thepresent invention wherein a thermosetting rubber is used,gradient-producing processes and/or gradient-producing rubberformulation may be employed. Gradient-producing processes andformulations are disclosed more fully, for example, in U.S. patentapplication Ser. No. 12/048,665, filed on Mar. 14, 2008; Ser. No.11/829,461, filed on Jul. 27, 2007; Ser. No. 11/772,903, filed Jul. 3,2007; Ser. No. 11/832,163, filed Aug. 1, 2007; Ser. No. 11/832,197,filed on Aug. 1, 2007; the entire disclosure of each of these referencesis hereby incorporated herein by reference.

Golf balls of the present invention will typically have dimple coverageof 60% or greater, preferably 65% or greater, and more preferably 75% orgreater.

The United States Golf Association specifications limit the minimum sizeof a competition golf ball to 1.680 inches. There is no specification asto the maximum diameter, and golf balls of any size can be used forrecreational play. Golf balls of the present invention can have anoverall diameter of any size. The preferred diameter of the present golfballs is from 1.680 inches to 1.800 inches. More preferably, the presentgolf balls have an overall diameter of from 1.680 inches to 1.760inches, and even more preferably from 1.680 inches to 1.740 inches.

Compression is an important factor in golf ball design. For example, thecompression of the core can affect the ball's spin rate off the driverand the feel. As disclosed in Jeff Dalton's Compression by Any OtherName, Science and Golf IV, Proceedings of the World Scientific Congressof Golf (Eric Thain ed., Routledge, 2002) (“J. Dalton”), severaldifferent methods can be used to measure compression, including Atticompression, Riehle compression, load/deflection measurements at avariety of fixed loads and offsets, and effective modulus. For purposesof the present invention, “compression” refers to Atti compression andis measured according to a known procedure, using an Atti compressiontest device, wherein a piston is used to compress a ball against aspring. The travel of the piston is fixed and the deflection of thespring is measured. The measurement of the deflection of the spring doesnot begin with its contact with the ball; rather, there is an offset ofapproximately the first 1.25 mm (0.05 inches) of the spring'sdeflection. Very low stiffness cores will not cause the spring todeflect by more than 1.25 mm and therefore have a zero compressionmeasurement. The Atti compression tester is designed to measure objectshaving a diameter of 42.7 mm (1.68 inches); thus, smaller objects, suchas golf ball cores, must be shimmed to a total height of 42.7 mm toobtain an accurate reading. Conversion from Atti compression to Riehle(cores), Riehle (balls), 100 kg deflection, 130-10 kg deflection oreffective modulus can be carried out according to the formulas given inJ. Dalton.

COR, as used herein, is determined according to a known procedurewherein a golf ball or golf ball subassembly (e.g., a golf ball core) isfired from an air cannon at two given velocities and calculated at avelocity of 125 ft/s. Ballistic light screens are located between theair cannon and the steel plate at a fixed distance to measure ballvelocity. As the ball travels toward the steel plate, it activates eachlight screen, and the time at each light screen is measured. Thisprovides an incoming transit time period inversely proportional to theball's incoming velocity. The ball impacts the steel plate and reboundsthough the light screens, which again measure the time period requiredto transit between the light screens. This provides an outgoing transittime period inversely proportional to the ball's outgoing velocity. CORis then calculated as the ratio of the outgoing transit time period tothe incoming transit time period, COR=V_(out)/V_(in)=T_(in)/T_(out).

Flexural modulus is measured using flex bars according to ASTM D790.

When numerical lower limits and numerical upper limits are set forthherein, it is contemplated that any combination of these values may beused.

All patents, publications, test procedures, and other references citedherein, including priority documents, are fully incorporated byreference to the extent such disclosure is not inconsistent with thisinvention and for all jurisdictions in which such incorporation ispermitted.

While the illustrative embodiments of the invention have been describedwith particularity, it will be understood that various othermodifications will be apparent to and can be readily made by those ofordinary skill in the art without departing from the spirit and scope ofthe invention. Accordingly, it is not intended that the scope of theclaims appended hereto be limited to the examples and descriptions setforth herein, but rather that the claims be construed as encompassingall of the features of patentable novelty which reside in the presentinvention, including all features which would be treated as equivalentsthereof by those of ordinary skill in the art to which the inventionpertains.

What is claimed is:
 1. A golf ball consisting essentially of: a centerhaving a diameter of less than 1.500 inches, a compression of from 5 to40, and formed from a polybutadiene composition; an outer cover layerformed from a composition having a flexural modulus of 40,000 psi orless; an intermediate layer disposed between the center and the outercover layer, the intermediate layer having an outer surface hardness ofgreater than 60 Shore D and being formed from a thermoplasticcomposition having a solid, single core compression of 60 or greater;wherein the outer surface hardness of the center and the outer surfacehardness of the outer cover layer are less than the outer surfacehardness of the intermediate layer; and wherein the solid, single corecompression of the intermediate layer is at least 25 compression pointshigher than the compression of the center.
 2. The golf ball of claim 1,wherein the polybutadiene composition of the center comprises from 0 to20 phr of a coagent selected from the group consisting of metal salts ofdiacrylates, dimethacrylates, and monomethacrylates.
 3. The golf ball ofclaim 1, wherein the thermoplastic composition of the intermediate layeris an ionomer composition.
 4. The golf ball of claim 1, wherein thethermoplastic composition of the intermediate layer is a highlyneutralized polymer composition.
 5. The golf ball of claim 1, whereinthe compression of the center is from 10 to
 40. 6. The golf ball ofclaim 1, wherein the solid, single core compression of the intermediatelayer is at least 30 compression points higher than the compression ofthe center.
 7. The golf ball of claim 1, wherein the diameter of thecenter is 1.300 inches or greater.
 8. The golf ball of claim 1, whereina golf ball subassembly consisting of the center and the intermediatelayer has a compression that is at least 30 compression points greaterthan the compression of the center.
 9. The golf ball of claim 8, whereinthe compression of the golf ball subassembly consisting of the centerand the intermediate layer is at least 40 compression points greaterthan the compression of the center.
 10. The golf ball of claim 8,wherein the compression of the golf ball subassembly consisting of thecenter and the intermediate layer is at least 50 compression pointsgreater than the compression of the center.